A Convenient Organic–Inorganic Hybrid Approach Toward Highly Stable Squaraine Dyes with Reduced H‐Aggregation
A Convenient Organic–Inorganic Hybrid Approach Toward Highly Stable Squaraine Dyes with Reduced H‐Aggregation
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DOI：
10.1002/adfm.201101565
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发表时间：
2012-01
影响因子：
19
通讯作者：
Zhengquan Yan;Hongyao Xu;Shanyi Guang;Xian Zhao;Weiliu Fan;X. Liu
中科院分区：
文献类型：
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作者：
Zhengquan Yan;Hongyao Xu;Shanyi Guang;Xian Zhao;Weiliu Fan;X. Liu
通过设计两种类型的含方酸菁的多面体低聚硅倍半硅氧烷（POSS）杂化物，探索了一种解决光学材料在固态或不良溶剂溶液中观察到的聚集效应的通用有效方法。通过共价键将“巨型”无机POSS纳米粒子引入到光学材料中，可以有效地降低偶极-偶极和π-π堆积作用，抑制相邻方酸分子间的电荷转移，提高材料的光学、热稳定性和化学稳定性。理论计算和实验结果均表明了分子设计策略的合理性和有效性。所得有机-无机杂化光学材料通过阻碍分子间电荷转移和减少发色团之间的偶极-偶极和π-π堆积相互作用，有效地消除了有机光学发色团的聚集，并表现出良好的光学稳定性，即，H1和H2的吸收峰仅显示轻微的蓝移，即使在固体中也是如此。与此同时，杂化材料的热稳定性和化学稳定性也比前体有机光学材料有显著提高。
A generic and effective approach for solving the aggregation effect observed with optical materials in solid state or in a solution with a poor solvent was explored by designing two types of squaraine‐containing polyhedral oligomeric silsesquoixane (POSS)‐based hybrids. It is expected that incorporation of “huge” inorganic POSS nanoparticles into optical materials via covalent bonding can effectively decrease the strong dipole–dipole and π–π stacking interactions, inhibit intermolecular charge transfer between adjacent squaraine molecules, and improve optical, thermal and chemical stability of the resultant materials. Both theoretical calculations and experimental results indicate that the molecular design strategy is rational and efficacious. The resultant organic–inorganic hybrid optical materials effectively eliminate the aggregation of organic optical chromophoric groups by hindering intermolecular charge transfer and decreasing dipole–dipole and π–π stacking interaction between the chromophores, and exhibit good optical stability, i.e., the absorption peaks of H1 and H2 display only a slight blue‐shift, even in the solid. Simultaneously, the hybrids also show significantly enhanced thermal, and chemical stabilities in comparison with the precursor organic optical materials.